DE60021204T2 - USE OF A PREMIX FOR THE PRODUCTION OF CORK - Google Patents
USE OF A PREMIX FOR THE PRODUCTION OF CORK Download PDFInfo
- Publication number
- DE60021204T2 DE60021204T2 DE60021204T DE60021204T DE60021204T2 DE 60021204 T2 DE60021204 T2 DE 60021204T2 DE 60021204 T DE60021204 T DE 60021204T DE 60021204 T DE60021204 T DE 60021204T DE 60021204 T2 DE60021204 T2 DE 60021204T2
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- Germany
- Prior art keywords
- weight
- use according
- cork
- polymer
- vinyl aromatic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000000203 mixture Substances 0.000 claims description 26
- 229920000642 polymer Polymers 0.000 claims description 19
- 229920002725 Thermoplastic elastomer Polymers 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 9
- 239000007799 cork Substances 0.000 claims description 9
- 239000004793 Polystyrene Substances 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 229920002223 polystyrene Polymers 0.000 claims description 7
- 239000003380 propellant Substances 0.000 claims description 7
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 6
- 150000001993 dienes Chemical class 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 239000000314 lubricant Substances 0.000 claims description 5
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 239000004604 Blowing Agent Substances 0.000 claims description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 229960003563 Calcium Carbonate Drugs 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L Calcium stearate Chemical group [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N Isobutane Chemical group CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 2
- 239000011324 bead Substances 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 239000001282 iso-butane Substances 0.000 claims description 2
- 239000010690 paraffinic oil Substances 0.000 claims description 2
- 238000010348 incorporation Methods 0.000 claims 1
- 239000007822 coupling agent Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 4
- 239000000806 elastomer Substances 0.000 description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N Butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- 229910003910 SiCl4 Inorganic materials 0.000 description 2
- FDNAPBUWERUEDA-UHFFFAOYSA-N Silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 235000019399 azodicarbonamide Nutrition 0.000 description 2
- VJRITMATACIYAF-UHFFFAOYSA-N benzenesulfonohydrazide Chemical compound NNS(=O)(=O)C1=CC=CC=C1 VJRITMATACIYAF-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000001808 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- XLHCFNYXQWSNAX-UHFFFAOYSA-N 1-N,4-N-dimethyl-1-N,4-N-dinitrobenzene-1,4-dicarboxamide Chemical compound [O-][N+](=O)N(C)C(=O)C1=CC=C(C(=O)N(C)[N+]([O-])=O)C=C1 XLHCFNYXQWSNAX-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N Azobisisobutyronitrile Chemical compound N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- XOZUGNYVDXMRKW-AATRIKPKSA-N Azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 1
- 239000004156 Azodicarbonamide Substances 0.000 description 1
- 229920001368 Crepe rubber Polymers 0.000 description 1
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- USVVENVKYJZFMW-UHFFFAOYSA-L N-carboxylatoiminocarbamate Chemical compound [O-]C(=O)N=NC([O-])=O USVVENVKYJZFMW-UHFFFAOYSA-L 0.000 description 1
- ZCIYMNRGYOCKQM-UHFFFAOYSA-N N-phenylbenzenesulfonohydrazide Chemical compound C=1C=CC=CC=1S(=O)(=O)N(N)C1=CC=CC=C1 ZCIYMNRGYOCKQM-UHFFFAOYSA-N 0.000 description 1
- ALIFPGGMJDWMJH-UHFFFAOYSA-N N-phenyldiazenylaniline Chemical compound C=1C=CC=CC=1NN=NC1=CC=CC=C1 ALIFPGGMJDWMJH-UHFFFAOYSA-N 0.000 description 1
- KVAFIKFDXQKQKO-UHFFFAOYSA-M N1=C(N)N=C(N)N=C1N.C([O-])(O)=O.[Na+] Chemical compound N1=C(N)N=C(N)N=C1N.C([O-])(O)=O.[Na+] KVAFIKFDXQKQKO-UHFFFAOYSA-M 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 229920001744 Polyaldehyde Polymers 0.000 description 1
- 229920002732 Polyanhydride Polymers 0.000 description 1
- 229920001228 Polyisocyanate Polymers 0.000 description 1
- 229920001470 Polyketone Polymers 0.000 description 1
- -1 Ureabiuret (33:67) Chemical compound 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium(0) Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- LDVAXRWOGUHMKM-UHFFFAOYSA-N benzene-1,3-disulfonohydrazide Chemical compound NNS(=O)(=O)C1=CC=CC(S(=O)(=O)NN)=C1 LDVAXRWOGUHMKM-UHFFFAOYSA-N 0.000 description 1
- YIYZHARUXWKUEN-UHFFFAOYSA-N benzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC=C1.NS(=O)(=O)C1=CC=CC=C1 YIYZHARUXWKUEN-UHFFFAOYSA-N 0.000 description 1
- LSNDGFYQJRXEAR-UHFFFAOYSA-N benzenesulfonamidourea Chemical compound NC(=O)NNS(=O)(=O)C1=CC=CC=C1 LSNDGFYQJRXEAR-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atoms Chemical group C* 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000001627 detrimental Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000005469 ethylenyl group Chemical group 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atoms Chemical class [H]* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 1
- OPTPEWSLEFFPTF-UHFFFAOYSA-N naphthalene-2-sulfonohydrazide Chemical compound C1=CC=CC2=CC(S(=O)(=O)NN)=CC=C21 OPTPEWSLEFFPTF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 229920002225 poly(styrene-co-butadiene) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- CLJTZNIHUYFUMR-UHFFFAOYSA-M sodium;hydrogen carbonate;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Na+].OC([O-])=O.OC(=O)CC(O)(C(O)=O)CC(O)=O CLJTZNIHUYFUMR-UHFFFAOYSA-M 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- HSVFKFNNMLUVEY-UHFFFAOYSA-N sulfuryl diazide Chemical compound [N-]=[N+]=NS(=O)(=O)N=[N+]=[N-] HSVFKFNNMLUVEY-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D39/00—Closures arranged within necks or pouring openings or in discharge apertures, e.g. stoppers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D39/00—Closures arranged within necks or pouring openings or in discharge apertures, e.g. stoppers
- B65D39/0005—Closures arranged within necks or pouring openings or in discharge apertures, e.g. stoppers made in one piece
- B65D39/0011—Closures arranged within necks or pouring openings or in discharge apertures, e.g. stoppers made in one piece from natural or synthetic cork, e.g. for wine bottles or the like
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/22—Expandable microspheres, e.g. Expancel®
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
Description
Gebiet der ErfindungTerritory of invention
Die vorliegende Erfindung betrifft die Verwendung eines Gemischs von Styrol-/Butadienelastomeren, Polystyrol, Öl und Additiven zur Produktion geformter Verschlüsse für Behälter.The The present invention relates to the use of a mixture of Styrene / butadiene elastomers, polystyrene, oil and additives for production shaped closures for containers.
Hintergrund der Erfindungbackground the invention
Im Stand der Technik sind bereits mehrere gummiartige Zusammensetzungen und deren Anwendungen beschrieben worden.in the The prior art already has several rubbery compositions and their applications have been described.
WO 96/16122 offenbart eine Zusammensetzung, die nützlich ist zur Herstellung von Elastomerartikeln wie etwa Folien, Fasern, gewebte und nicht-gewebte Artikel. Die Zusammensetzung umfasst thermoplastische Elastomere, vermischt mit anderen Polymeren, um ihre Verarbeitung zu verbessern.WHERE 96/16122 discloses a composition useful for preparation of elastomeric articles such as films, fibers, woven and non-woven Items. The composition comprises thermoplastic elastomers, mixed with other polymers to improve their processing.
Das US-Patent 4.306.034 betrifft gummiartige Zusammensetzungen und daraus geformte Polymerartikel, die das Aussehen natürlichen Plantagenkreppgummis fördern. Diese Zusammensetzungen umfassen beispielsweise Polarisationsmittel.The U.S. Patent 4,306,034 relates to and from rubbery compositions molded polymer articles that look like natural plantation crepe rubber promote. These compositions include, for example, polarizers.
Die
Derwent-Zusammenfassung von
Die
Derwent-Zusammenfassung von
Die
Derwent-Zusammenfassung von
Das Verschließen von Behältern, insbesondere Weinflaschen, wird zu einem wichtigen Thema, da die Zufuhr von Naturkork nicht mit der erhöhten Nachfrage für Weinflaschenabfüllung in verschiedenen Teilen der Welt Schritt hält.The close of containers, especially wine bottles, becomes an important topic as the feed of natural cork not with the raised Demand for Wine bottling keeps pace in different parts of the world.
Es wurden mehrere Versuche unternommen, um Naturkork durch synthetische Materialien zu ersetzen. Diese Versuche basieren auf Rezepturen, die unter anderem zum Vermischen mit einem Treibmittel geeignet sind. Die Rolle besagten Treibmittels ist es, die Erzeugung von Zellen, die das Zellverhalten von Naturkork kopieren, zu gestatten. Unter den von diesen Versuchen herrührenden Nachteilen kann man beispielsweise den Mangel an Gleichförmigkeit des aufgeschäumten Harzes anführen, der zum Lecken der Behälter führt, oder die Notwendigkeit der Verwendung von Additiven, wie etwa Schwefeldioxid als Sauerstoffaufnehmer, die nachteilig für die Qualität der enthaltenen Flüssigkeit sind.It Several attempts have been made to synthetic cork by synthetic To replace materials. These experiments are based on formulas, which is suitable inter alia for mixing with a propellant are. The role of said propellant is to prevent the generation of Allow cells that copy the cell behavior of natural cork. Among the disadvantages of these experiments one can For example, the lack of uniformity of the foamed resin adduce which leads to the leaking of the containers, or the need to use additives such as sulfur dioxide as an oxygen scavenger, which is detrimental to the quality of the contained liquid are.
Es sind bestimmte Polymere verwendet worden, um eine Verbesserung zu bringen. US-5.855.287 beschreibt somit einen synthetischen Verschluss, der hydrierte Styrol-Butadiencopolymere und zumindest 1 Gew.% eines Treibmittels umfasst.It Certain polymers have been used to improve bring. US 5,855,287 thus describes a synthetic closure, the hydrogenated styrene-butadiene copolymer and at least 1% by weight of a propellant.
Obwohl dieser Verschluss seinen Zweck erreicht, ist er in Hinblick auf die relativ hohen Kosten der verwendeten Rohmaterialien noch stets nicht zufriedenstellend.Although this closure achieves its purpose, it is in view of the relatively high cost of ver Raw materials were still unsatisfactory.
Zusammenfassung der Erfindung:Summary of the invention:
Es ist ein Ziel der vorliegenden Erfindung, eine Verbesserung in Begriffen von Rohmaterialersparnis zu erzielen, während gleiche oder überlegene mechanische Eigenschaften verschafft werden.It An object of the present invention is an improvement in terms to achieve raw material savings while same or superior mechanical properties are procured.
Erfindungsgemäß wird dieses Problem durch die Verwendung eines Gemischs gelöst, das a) 20 bis 60 Gew.% eines thermoplastischen Elastomers, das von der Copolymerisation eines vinylaromatischen Monomers und eines konjugierten Diens herrührt und 20 bis 80 Gew.% des vinylaromatischen Polymers und 80 bis 20 Gew.% des Butadienpolymers enthält, und b) 8 bis 30 Gew.% eines vinylaromatischen Polymers, und c) 10 bis 30 Gew.% eines oder mehr Verarbeitungshilfsmittel, und d) 0 bis 20 Gew.% eines oder mehr Additive umfasst. Das Gemisch wird zur Herstellung von Muttermischungen verwendet, die, nach dem Vermischen mit einem Treibmittel, für die Produktion von Verschlüssen für Flüssigkeitsbehälter, wie etwa Flaschen, geeignet sind.According to the invention this Problem solved by the use of a mixture containing a) 20 to 60% by weight a thermoplastic elastomer derived from the copolymerization a vinyl aromatic monomer and a conjugated diene, and 20 to 80% by weight of the vinylaromatic polymer and 80 to 20% by weight of the butadiene polymer, and b) 8 to 30% by weight of a vinyl aromatic polymer, and c) 10 to 30% by weight of one or more processing aids, and d) 0 to 20% by weight of one or more additives. The mixture becomes Preparation of mother mixes used, after mixing with a propellant, for the production of closures for liquid containers, like about bottles, are suitable.
Die in Übereinstimmung mit der Erfindung verwendeten Gemische können an eine breite Vielfalt von Verarbeitungshilfsmitteln, Additiven und Treibmitteln angepasst werden. Sie verschaffen gute mechanische Eigenschaften und können in vielen Anwendungen, die einen dichten Verschluss für Flüssigkeitsbehälter, wie etwa Flaschen, erfordern, verwendet werden.The in accordance Mixtures used with the invention are capable of a wide variety adjusted by processing aids, additives and blowing agents become. They provide good mechanical properties and can be used in Many applications require a tight seal for liquid containers, such as Bottles, require, to be used.
Unter den thermoplastischen Elastomeren, die in Übereinstimmung mit der vorliegenden Erfindung verwendet werden können, werden die von besonderer Wichtigkeit gemäß einem in Lösung betriebenen Prozess produziert.Under the thermoplastic elastomers used in accordance with the present invention Invention can be used become of particular importance according to a solution operated Process produced.
Ein solcher Prozess ist in der Technik bekannt, es wird auf EP-A-0084795 und EP-B-344140 verwiesen.One such process is known in the art, it is referred to EP-A-0084795 and EP-B-344140.
Das besonders bevorzugte vinylaromatische Monomer ist Styrol und das bevorzugte konjugierte Dien ist Butadien.The Particularly preferred vinyl aromatic monomer is styrene and the preferred conjugated diene is butadiene.
Diese Monomere werden in Gegenwart von Initiatoren oder Katalysatoren, die im allgemeinen unverzweigtes oder verzweigtes Alkyllithium mit 3 bis 8 Kohlenstoffatomen sind, der Polymerisation unterzogen. Jedoch werden vorzugsweise n- und s-Butyllithium verwendet.These Monomers are in the presence of initiators or catalysts, the generally unbranched or branched alkyllithium with 3 to 8 carbon atoms are subjected to the polymerization. however For example, n- and s-butyllithium are preferably used.
Es wird ein Kopplungsmittel verwendet, um eine spezifische Molekularkonfiguration des resultierenden Polymers zu gestatten. Das Kopplungsmittel kann aus Polyvinylverbindungen, Polyepoxiden, Polyisocyanaten, Polyaminen, Polyaldehyden, Polyhaliden, Polyanhydriden, Polyketonen, Polyepoxyestern und Polyestern gewählt werden. Unter den mehreren polyfunktionellen Kopplungsmitteln werden diejenigen mit geringer Resttoxizität bevorzugt. Beispielsweise offenbart EP-B-344140 die Verwendung eines polyfunktionellen Kopplungsmittels mit der allgemeinen Formel SiXnR4-n, wobei X ein Halogen, vorzugsweise Cl, ist; R ein Alkyl, Cycloalkyl oder Arylradikal, vorzugsweise Methyl, Ethyl und/oder Phenyl, ist; und n eine ganze Zahl von 2 bis 4 ist. Das am häufigsten verwendete Kopplungsmittel ist SiCl4. Es ist auch bekannt, organische Kopplungsmittel zu verwenden, die Epoxygruppen tragen. Es werden Polymere epoxidierter Kohlenwasserstoffe verwendet, wie etwa epoxidierte Pflanzenöle, wie etwa epoxidiertes Sojaöl und epoxidiertes Leinöl.It For example, a coupling agent is used to give a specific molecular configuration of the resulting polymer. The coupling agent can from polyvinyl compounds, polyepoxides, polyisocyanates, polyamines, Polyaldehydes, polyhalides, polyanhydrides, polyketones, polyepoxyesters and polyesters are chosen become. Among the several polyfunctional coupling agents those with low residual toxicity are preferred. For example EP-B-344140 discloses the use of a polyfunctional coupling agent with the general formula SiXnR4-n, where X is a halogen, preferably Cl, is; R is an alkyl, cycloalkyl or aryl radical, preferably methyl, Ethyl and / or phenyl; and n is an integer from 2 to 4. The most common Coupling agent used is SiCl4. It is also known organic To use coupling agents that carry epoxy groups. It will Polymers of epoxidized hydrocarbons used, such as epoxidized Vegetable oils, such as epoxidized soybean oil and epoxidized linseed oil.
Das Styrol-Butadienelastomer kann weiter einer Hydrationsbehandlung unterzogen werden, um die verbleibenden Doppelbindungen zu entfernen, wodurch sich ein Copolymer von Polystyrol-Polyethylen-Butylen-Polystyrol ergibt.The Styrene-butadiene elastomer may further undergo a hydration treatment be subjected to remove the remaining double bonds, resulting in a copolymer of polystyrene-polyethylene-butylene-polystyrene.
Die Styrolmenge in dem Elastomer kann zwischen 25 und 80 Gew.% variieren, was es in Kombination mit dem Kopplungsmittel gestattet, erforderliche Merkmale wie etwa Härte, Ausdehnung und Stärke auszuwählen.The Styrene level in the elastomer may vary between 25 and 80 weight percent, what is required in combination with the coupling agent required Characteristics such as hardness, Extension and strength select.
Das Vorhandensein von 8 bis 25 Gew.% eines vinylaromatischen Polymers, vorzugsweise Polystyrol, ist ebenfalls erforderlich. Eine Mischung von hochschlagfestem Polystyrol und Polystyrol für allgemeine Verwendung wird bevorzugt, um die erforderliche Härte zu erzielen.The Presence of 8 to 25% by weight of a vinylaromatic polymer, preferably polystyrene, is also required. A mixture of high impact polystyrene and polystyrene for general use preferred to achieve the required hardness.
Das Vorhandensein von 15 bis 27 Gew.% eines Verarbeitungshilfsmittels ist erforderlich. Es können mehrere Öle verwendet werden, wie etwa eine Mischung von naphthenischem und paraffinischem Öl. Die Rolle dieser Hilfsmittel ist das Senken der Viskosität der Muttermischung, wodurch eine verbesserte Verarbeitungsgeschwindigkeit gestattet wird.The presence of 15 to 27% by weight of a processing aid is required. Several oils can be used, such as a mixture of naphthenic and paraffinic oils. The Rol This aid is to lower the viscosity of the masterbatch, thereby allowing an improved processing speed.
Optionsweise können ein oder mehr Additive in einer Menge von bis zu 20 Gew.% verwendet werden. Manche Additive, auch Füllstoffe genannt, werden zur Senkung der Produktionskosten der Muttermischung verwendet. Unter den vielen, den Fachleuten bekannten Füllstoffen ist ein bevorzugtes Material Calciumcarbonat in einer Menge von weniger als 15 Gew.%, vorzugsweise weniger als 10 Gew.%. Manche anderen Additive, auch Gleitmittel genannt, werden zur Verbesserung des Einbringens des Korkens in die Behälter verwendet. Unter den Gleitmitteln können wir Salze von Fettsäuren, wie etwa Calciumstearat, anführen.Optionally, can one or more additives in an amount of up to 20 wt.% Used become. Some additives, including fillers are used to reduce the production costs of the mother mix. Among the many fillers known to those skilled in the art is a preferred one Material calcium carbonate in an amount of less than 15% by weight, preferably less than 10% by weight. Some other additives, too Lubricants are called to improve the introduction of the Cork in the containers used. Among the lubricants we can find salts of fatty acids, such as about calcium stearate, lead.
Das vorliegende Gemisch ist besonders zum Vermischtwerden mit Treib- oder Aufschäummitteln geeignet, die die Produktion von Zellen innerhalb des Verschlusses gestatten. Diese Mittel können vom chemischen oder physikalischen Typ oder eine Kombination davon sein. Unter den chemischen Mitteln kann man Diazoaminobenzol, Benzolsulfosäurehydrazid, N,N'-Dimethyl-N,N'-Dinitroterephthalamid, Azobisisobutyronitril, Tetramethylendinitrosodimethylurethan, p,p-Oxybis(N-nitroso-N-methyl)benzolsulfonamid, Ureabiuret (33:67), β-Naphthalensulfosäurehydrazid, Natriumbicarbonat-Zitronensäure (4:3), Natriumbicarbonat-Melamin (95:5), Benzol-1,3-Disulfosäuredihydrazid, 1,6-Di-n-decyl-azobisformamid, Biphenyl-4,4'-di(sulfonylazid), Benzolsulfosäure-N-phenylhydrazid, Diphenylsulfon-3,3'-disulfonylhydrazid, p,p'-Oxybis(benzolsulfonylhydrazid), 1,6-Diphenylazobisformamid, Dinitrosopentamethylentetramin, Azodicarbonamid, p,p-Oxybis(benzensulfonylsemicarbazid), Bariumazodicarboxylat anführen. Unter dem physikalischen Typ kann man Wasserstoff, Luft, Stickstoff, Kohlendioxid, Wasserdampf, Kohlenwasserstoffe, sauerstoffhaltige Aliphate, chlorierte Kohlenwasserstoffe, Chlorfluorkohlenwasserstoffe anführen. Ein besonders bevorzugtes Mittel ist ein Isobutan enthaltendes Polyacrylnitrilpolymerkügelchen.The present mixture is particularly suitable for mixing with propellant or foaming agents suitable for the production of cells within the closure allow. These funds can of the chemical or physical type or a combination thereof be. Among the chemical agents, diazoaminobenzene, benzenesulfonic acid hydrazide, N, N'-dimethyl-N, N'-Dinitroterephthalamid, Azobisisobutyronitrile, tetramethylenedinitrosodimethylurethane, p, p-oxybis (N-nitroso-N-methyl) benzenesulfonamide, Ureabiuret (33:67), β-naphthalenesulfonic acid hydrazide, Sodium bicarbonate-citric acid (4: 3), sodium bicarbonate-melamine (95: 5), benzene-1,3-disulphonic dihydrazide, 1,6-di-n-decyl azobisformamide, Biphenyl-4,4'-di (sulfonyl azide), benzenesulfonic acid N-phenylhydrazide, Diphenyl-3,3'-disulfonylhydrazide, p, p'-oxybis (benzenesulfonyl hydrazide) 1,6-diphenylazobisformamide, dinitrosopentamethylenetetramine, azodicarbonamide, p, p-oxybis (benzenesulfonyl semicarbazide), barium azodicarboxylate. Under the physical type can be hydrogen, air, nitrogen, carbon dioxide, Water vapor, hydrocarbons, oxygen-containing aliphatics, chlorinated Hydrocarbons, lead chlorofluorocarbons. One Particularly preferred agent is an isobutane-containing polyacrylonitrile polymer bead.
Diese Verbindung ist im Handel unter dem Markennamen Expancell, hergestellt von AKZO, Niederlande, erhältlich.These Compound is manufactured under the trade name Expancell from AKZO, The Netherlands.
Überraschenderweise hat der Erfinder festgestellt, dass die vorliegenden Gemische das Erzielen hoher mechanischer Eigenschaften gestatten, während sie in der Lage sind, mit einer Verschiedenheit von Aufschäummitteln vermischt zu werden. Das Gemisch ist daher ein idealer Kandidat für mehrere Anwendungen auf dem Gebiet von Verschlüssen für flüssigkeitsenthaltende Verpackungen.Surprisingly the inventor has found that the present mixtures the Allowing high mechanical properties while they do are able to with a variety of foaming agents to be mixed. The mixture is therefore an ideal candidate for many Applications in the field of closures for liquid containing packaging.
Das folgende Beispiel illustriert die Erfindung. Dieses Beispiel wird jedoch nur als Anleitung gegeben und impliziert keinerlei Einschränkungen.The The following example illustrates the invention. This example will but only as a guide and does not imply any restrictions.
Beispiel:Example:
Es wurden mehrere Gemische hergestellt, die Styrol-Butadienelastomere enthielten.It Several blends were prepared containing styrene-butadiene elastomers.
Finaprene 507 ist ein lineares SBS, das 73% PS enthält. Sein MFI bei 190°C/5kg beträgt 7,5 g/10 min.Finaprene 507 is a linear SBS that contains 73% horsepower. Its MFI at 190 ° C / 5kg is 7.5g / 10 minute
Finaprene 435 ist ein radiales SBS (SiCl4-Kopplung), das 31% PS enthält.Finaprene 435 is a radial SBS (SiCl4 coupling) containing 31% PS.
Finaprene 602F ist ein radiales SBS (Vikoflex-Kupplung), das 40% PS enthält. Sein MFI bei 190°C/5 kg beträgt 8,5 g/10 min.Finaprene 602F is a radial SBS (Vikoflex coupling) that contains 40% horsepower. Be MFI at 190 ° C / 5 kg is 8.5 g / 10 min.
Die folgenden Verfahren wurden zum Messen der in diesen Beispielen erscheinenden Eigenschaften verwendet:
- 1. Härtegrad Shore : ASTM-D 2240
- 2. Abrieb : DIN 53516
- 3. Schmelzfluss (M15) : ASTM-D 1238, revidiert 89, auf 190°C und unter einer Belastung von 5 kg.
- 4. Zug und Verlängerung : ASTM-D 412, D 638, D882
- 1. Hardness Shore: ASTM-D 2240
- 2. Abrasion: DIN 53516
- 3. Melt flow (M15): ASTM-D 1238, revised 89, to 190 ° C and under a load of 5 kg.
- 4. Pull and extension: ASTM-D 412, D 638, D882
Claims (11)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP99124497A EP1106650A1 (en) | 1999-12-08 | 1999-12-08 | Blend for masterbatches |
EP99124497 | 1999-12-08 | ||
PCT/EP2000/012869 WO2001042354A1 (en) | 1999-12-08 | 2000-12-07 | Blend for masterbatches |
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DE60021204D1 DE60021204D1 (en) | 2005-08-11 |
DE60021204T2 true DE60021204T2 (en) | 2006-05-11 |
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DE60021204T Expired - Fee Related DE60021204T2 (en) | 1999-12-08 | 2000-12-07 | USE OF A PREMIX FOR THE PRODUCTION OF CORK |
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US (1) | US6852764B2 (en) |
EP (2) | EP1106650A1 (en) |
JP (1) | JP2003516454A (en) |
CN (1) | CN1194037C (en) |
AT (1) | AT299166T (en) |
AU (1) | AU783552B2 (en) |
CA (1) | CA2392588A1 (en) |
DE (1) | DE60021204T2 (en) |
ES (1) | ES2243342T3 (en) |
HU (1) | HU0203838A2 (en) |
WO (1) | WO2001042354A1 (en) |
ZA (1) | ZA200204034B (en) |
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US7997439B2 (en) | 2003-06-06 | 2011-08-16 | Jamak Fabrication-Tex, Llc | Flexible bakeware having a multi-piece carrier system |
US7966970B2 (en) | 2005-07-19 | 2011-06-28 | M Management-Tex, Llc | Dairy inflation |
JP5171238B2 (en) * | 2007-12-18 | 2013-03-27 | 大日精化工業株式会社 | Foaming agent masterbatch |
US10577487B2 (en) * | 2016-05-06 | 2020-03-03 | Canon Kabushiki Kaisha | Thermoplastic resin composition, molded article, and manufacturing method of molded article |
JP2019019163A (en) * | 2017-07-12 | 2019-02-07 | 東洋スチレン株式会社 | Styrenic resin composition and molding prepared therewith |
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GB1196127A (en) * | 1966-09-30 | 1970-06-24 | Grace W R & Co | Thermoplastics Compositions |
FR2114383A5 (en) * | 1970-11-13 | 1972-06-30 | Basf Ag | |
US4306034A (en) * | 1978-09-19 | 1981-12-15 | Phillips Petroleum Company | Composition for producing article simulating plantation crepe rubber |
GB2147906A (en) * | 1983-10-13 | 1985-05-22 | Shell Int Research | Block copolymer compositions |
JPH0657765B2 (en) * | 1986-04-30 | 1994-08-03 | 旭化成工業株式会社 | Highly filled composition |
JPS63118359A (en) * | 1986-06-27 | 1988-05-23 | Nippon Erasutomaa Kk | Thermoplastic elastomer composition |
JPH0412900B2 (en) * | 1986-08-29 | 1992-03-06 | Asahi Chemical Ind | |
US5496862A (en) * | 1993-05-05 | 1996-03-05 | Supreme Corq | Molded styrene block copolymer closure for a wine container |
ES2121435T3 (en) * | 1994-11-22 | 1998-11-16 | Dow Chemical Co | USEFUL COMPOSITION FOR ELASTOMERIC ARTICLES AND ARTICLES PREPARED FROM THE COMPOSITION. |
US6085923A (en) * | 1996-08-13 | 2000-07-11 | Neocork Technologies, Inc. | Composite synthetic stopper |
EP1166991B1 (en) * | 2000-06-22 | 2006-02-22 | Mitsui Chemicals, Inc. | Process, machine and composition for injection foaming |
-
1999
- 1999-12-08 EP EP99124497A patent/EP1106650A1/en not_active Withdrawn
-
2000
- 2000-12-07 WO PCT/EP2000/012869 patent/WO2001042354A1/en active IP Right Grant
- 2000-12-07 EP EP00988801A patent/EP1238010B1/en not_active Expired - Lifetime
- 2000-12-07 JP JP2001543645A patent/JP2003516454A/en active Pending
- 2000-12-07 ES ES00988801T patent/ES2243342T3/en not_active Expired - Lifetime
- 2000-12-07 AT AT00988801T patent/AT299166T/en not_active IP Right Cessation
- 2000-12-07 CA CA002392588A patent/CA2392588A1/en not_active Abandoned
- 2000-12-07 DE DE60021204T patent/DE60021204T2/en not_active Expired - Fee Related
- 2000-12-07 HU HU0203838A patent/HU0203838A2/en unknown
- 2000-12-07 CN CN 00816879 patent/CN1194037C/en not_active Expired - Fee Related
- 2000-12-07 US US10/149,091 patent/US6852764B2/en not_active Expired - Fee Related
- 2000-12-07 AU AU25117/01A patent/AU783552B2/en not_active Ceased
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- 2002-05-21 ZA ZA200204034A patent/ZA200204034B/en unknown
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ZA200204034B (en) | 2003-08-21 |
CN1194037C (en) | 2005-03-23 |
HU0203838A2 (en) | 2003-04-28 |
EP1106650A1 (en) | 2001-06-13 |
AT299166T (en) | 2005-07-15 |
CN1409741A (en) | 2003-04-09 |
ES2243342T3 (en) | 2005-12-01 |
EP1238010B1 (en) | 2005-07-06 |
AU783552B2 (en) | 2005-11-10 |
DE60021204D1 (en) | 2005-08-11 |
CA2392588A1 (en) | 2001-06-14 |
JP2003516454A (en) | 2003-05-13 |
WO2001042354A1 (en) | 2001-06-14 |
US20030050353A1 (en) | 2003-03-13 |
US6852764B2 (en) | 2005-02-08 |
EP1238010A1 (en) | 2002-09-11 |
AU2511701A (en) | 2001-06-18 |
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